Working of metals with salts of amine carboxylic acids and amine alkyl phosphate



United States Patent WORKING OF METALS WITH SALTS OF AMINE CARBOXYLICACIDS AND AMINE ALKYL PHOSPHATE Fletcher Thorne Thomsen, Shreveport,La., and Warren J. Miller, Waskom, Tern, assignors to Universal OilProducts Company, Des Plaines, 11]., a corporation of Delaware NoDrawing. Filed Mar. 6, 1963, Ser. No. 263,119

8 Claims. (Cl. 7242) This invention relates to the working of metals andmore particularly to the use of a novel drawing compound therein.

Reference to the working of metals is considered in a generic sense inthe industry to describe various operations performed on metalsincluding drawing, stamping, rolling, forging, heading, extruding,cupping, forming, bending, seaming, curling, sizing, swaging, embossing,coining, spinning, punching, piercing, parting, shearing, splitting,lancing, trimming, shaving, broaching, drinking, burring, cutting,machining, grinding, etc. The specific method of working will vary withthe individual machine shop, press shop, foundry, fabricator, etc., tosuit its particular apparatus and requirements. It is understood thatthis term is used in a like manner in the present specification andclaims to include one or more of the above operations.

' In the working of metals it is important that certain steps be takento insure efficient operation. Because the working operation involvesthe contact of two different metals (the die and the metal beingworked), it is of importance to utilize a lubricant to avoid seizure,fusion, attrition of the metals, etc. Also, it is important to utilize acooling medium to dissipate the heat of friction caused by the contactof the metals. Various liquids, pastes, flakes or compositionsheretofore have been used to serve both as a lubricant and coolant,these being known in the industry as drawing compounds. The presentinvention provides a novel drawing compound which serves as an effectivelubricant and coolant and, in addition, also serves to retard corrosionof the formed metal. This is important because the formed articlegenerally is stored prior to shipment and may undergo corrosion duringsuch storage or it may undergo corrosion during the shipment. Anotherimportant advantage to the use of the novel drawing compound of thepresent invention is that it also protects the die against corrosionwhich Otherwise may occur, particularly while standing during shutdown.In addition, the novel drawing compound offers other importantadvantages, as will be hereinafter set forth.

The novel drawing compound of the present invention is used in theworking of any suitable metal or alloy, including both ferrous andnon-ferrous. Illustrative but not limiting examples include low-carbonsteel, highcarbon steel, sheet steel, cast iron, aluminum, tungsten,magnesium, tin, copper, titanium, vanadium, nickel, platinum, silver,etc., and alloys including, for example, brass, bronze, etc. These maybe formed into various parts including, for example, wire, tubing,automotive body parts such as doors, tops, cowls, frames, springsuspension parts, bumper brackets, bearings, wheels, brag: bands, clutchplates, electrical contacts, etc., parts for metal furniture,refrigerator parts, machine parts, typewriter parts, adding machineparts, railroad and aircraft parts, handles for doors and drawers, etc.,internal equipment for reaction chambers, fractionating columns, heatexchangers, pumps, etc. It is understood that these are but a few of themany diversified metal parts that are formed by working in the mannerhereinafter set forth,

N-alkyl-1,5-diaminohexane,

ice

and that the novel drawing compound of the present invention is used inany metal working operation.

While the novel drawing compound of the present invention can be used insome instances in the hot working of metals, it is particularly usefulin cold working processes. In the latter operation, it is important thatthe drawing compound serves effectively as a lubricant and also as acoolant to dissipate the heat of friction created upon contact of themetals. Also, it is of extreme importance that the metals be protectedagainst corrosion. In addition, as hereinbefore set forth, the noveldrawing compound offers other important ad vantages to be describedhereinafter.

Inone embodiment the present invention relates to the method of workinga metal which comprises effecting said working in the presence of adrawing compound containing (1) salt of amine having at least 8 carbonatoms and carboxylic acid having at least 6 carbon atoms and (2) salt ofamine having at least 8 carbon atoms and alkyl acid phosphate in whichat least 1 alkyl group contains at least 3 carbon atoms.

From the hereinbefore embodiment, it will be seen that the novel drawingcompound contains a mixture of two different amine salts. This mixtureof amine salts is hydrocarbon soluble and preferably is formed as asolution in a suitable hydrocarbon oil in the manner to be hereinafterset forth. In another embodiment the mixture of salts may beincorporated as an additive in conventional drawing compounds and servesto impart therein the important advantages herein set forth.

One component of the drawing compound of the present invention is anamine salt of a carboxylic acid. Any suitable amine may be employed andmay comprise a primary mon-oamine, but preferably comprises a di-amineand, still more particularly, an N-alkyl-diaminoalkane. Preferably, theamine contains at least 8 carbon atoms and, in general, will containfrom about 12 to about 40 carbon atoms per molecule. Illustrativeprimary monoamines include octylamine, nonylamine, decylamine,undecylamine, dodecylamine, tridecylamine, tetradecylamine,pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine,nonadecylamine, eicosylamine, etc. The amine may be prepared from fattyacid derivatives and thus may comprise tallow amine, hydrogenated tallowamine, lauryl amine, coconut amine, soya amine, etc.

Of the diamines, the N-alkyl-diaminoalkanes are preferred. Aparticularly preferred amine of this class comprises anN-alkyl-1,3-diaminopropane in which the alkyl group contains from about8 to about 25 carbon atoms. A number of N-alkyl-1,3-diaminopropanes ofthis class are available commercially, such as Duomeen T and Diam 26 inwhich the alkyl group is derived from tallow and contains from about 12to about 20 carbon atoms per group, and mostly 16 to 18 carbon atoms.Other N-alkyl-1,3-diaminopropanes may be prepared to contain any numberof carbon atoms desired in the alkyl group and thus the alkyl group isselected from hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,nonadecyl, eicosyl, etc.

While the N-alkyl-1,3-diaminopropanes are preferred, it is understoodthat other suitable N-alkyl-diaminoalkanes may be employed. Illustrativeexamples include N-alkyl-l,2 diaminoethane, Naalkyl-1,2-diaminopropane,N-alkyl-l,Z-diaminobutane, N-alkyl 1,3-diaminobutane,N-alkyl-1,4-diaminobutane, N-alkyl-1,2-diaminopentane,N-allcyl-1,3-diaminopentane, N-alkyll,4-diaminopentane,N-alkyl-1,5-diarninopentane, N-alkyl-l,2,-diaminohexane, N-alkyl1,3-diaminohexane, N-alkyl-1,4-diaminohexane,

N alkyld,6-diaminohexane,

etc. It is understood that a mixture of amines may be employed and alsothat the different amines are not necessarily equivalent but all of themmay be used in the preparation of active compositions.

As hereinbefore set forth, the amine salt of a carboxylic acid is usedas one component of the mixture. Any suitable carboxylic acid is used,preferably a polybasic carboxylic acid. The carboxylic a-cid preferablycontains at least 6 and still more preferably at least 10 carbon atomsper molecule and, m-ore particularly, from about to about 50 carbonatoms per molecule. Illustrative polybasic carboxylic acids includeadipic, pimelic, suberic, azelaic, sebacic, phthalic, etc., aconitic,citric, etc., hemimellitic, trimesic, prehnitic, mellophanic,pyromellitic, mellitic, etc., and higher molecular polybasic carboxylicacids. It is understood that a mixture of acids may be employed.

A particularly preferred acid comprises a mixed byproduct acid beingmarketed commercially under the trade name of VR-l Acid. This acid is amixture of polybasic acids, predominantly dibasic, and is a residueproduced by distilling, at about 270 C. under about 4 mm. of mercurypressure, the by-product acids obtained in the preparation of sebacicacid by fusing castor oil with alkali. Production of this residue isdescribed in more detail in US. Patent 2,267,269 to Cheetham et al. Inthe manufacture of sebacic acid from castor oil, the oil is heated witha caustic alkali. This splits the oil, forming octanol-2, methylhexylketone, the alkali salt of sebacic acid, and the alkali salts of variousother longchained acids. The alcohol and ketone are readily removed fromt-he reaction mixture by distillation. The alkali salts which remainthen are dissolved in water and, upon slight acidification of theresulting solution, an oily layer separates. At a pH of about 6, theaqueous phase contains the alkali salt of sebacic acid, while the oilylayer contains various other acids from the reaction. The termby-product acids is generally applied to the mixture of acids formingthe oily layer.

These by-product acids then are separated into two parts. After theseacids have been washed with a dilute mineral acid, such as sulfuric orhydrochloric, they are washed with water and dried. They then aredistilled under reduced pressure. Fatty acids which are primarilymonobasic carboxylic acids are taken off at 100 C. to 270 C. atpressures as low as 4 mm. This treatment leaves a residue which is amixture of fatty acids, apparently primarily polybasic in character. Theresidue is commercially available from Rohm & Haas Company under thetrade name of VR-l Acid and has an average molecular weight of 500-600,an acid number of 134-160, a saponification number of 174-179, and aniodine number of 53-60. Another mixed acid of substantially the samecomposition is available commercially under the trade name of DSOMEAcid.

Another preferred acid comprises a mixed acid being marketedcommercially under the trade name of Empol 1022. This dimer acid is adilinoleic acid and is represented by the following general formula:

This acid is a viscous liquid, having an apparent molecular weight ofapproximately 600. It has an acid value of 180-192, an iodine value of80-95, a saponification value of 185-195, a neu-tralizaiton equivalentof 290-310, a refractive index at C. of 1.4919, a specific gravity atl5.5 C./\15.5 C. of 0.95, a flash point of 530 F., a fire point of 600F., and a viscosity at 100 C. of 100 centistokes.

While the polycarboxylic acids generally are preferred, in anotherembodiment of the invention a monocarboxylic acid may be used or amixture of a monocarboxylic acid and the polycarboxylic acidhereinbefor'e set forth.

Here again, it is preferred that the carboxylic acid contains at least 6atoms per molecule and may range up to carbon atoms per molecule.Illustrative monocarboxylic acids include caproic, heptylic, caprylic,pelargonic, capric, lauric, myristic, palmitic, stearic, arachidic,behenic, lignoceric, cerotic, etc., decalenic, dodecalenic, pahnitoleic,oleic, ricinoleic, petroselinic, vaccenic, linoleic, linolenic,eleostearic, licanic, parinaric, gadoleic, arac-hidonic, cetoleic,erucic, selacholei-c, etc.

Here again, mixtures of such acids are available commercially at lowercost and advantageously are used in preparing the drawing compound ofthe present invention. A particularly preferred mixture is tall oil acidwhich comprises a mixture of saturated and unsaturated fatty acids androsin acids and is obtained by acidifying the black liquor skimmingsobtained in the pulping of wood. The manufacture of tall oil acid isdescribed in the Encyclopdeia of Chemical Technology, volume 13, pages572-577. A number of typical American tall oil acids are shown on page575 of this encyclopedia, along with typical properties thereof.

While the crude tall oil acid may be used in accordance with the presentinvention, it is preferable to use a purified tall oil acid. Aparticularly satisfactory tall oil acid is available commercially underthe trade name of Indusoil L-S. properties:

This acid has the following typical Specifications Minimum MaximumColor, Gardner Acid N o Saponifieation No Fatty acids, perce Rosinacids, percent- Unsaponifiahles, percent Specific gravity, F/60F PourPoint, F Flash Point, Open Cup. Fire Point, Open Cup, F

When a mixture of the monocarboxylic acid and the polycarboxylic acid isused, both being selected from those hereinbefore set forth, itgenerally is preferred to use these in a ratio of one equivalent of eachwith two equivalents of the amine. However, in some cases, an excess ofone acid may be employed and thus may range up to ten or moreequivalents of the monocarboxylic acid with one equivalent of thepolycarboxylic acid, or up to ten or more equivalents of thepolycarboxylic acid with one equivalent of the monocarboxylic acid.

The amine salt of carboxylic acid is prepared in any suitable manner. Ingeneral, the salt is readily prepared by admixing the amine andcarboxylic acid at ambient temperature, preferably with vigorousstirring. Elevated temperature may be employed, but generally will notexceed about 250 F. When desired, the salt may be prepared in thepresence of a solvent for ease in handling, either of the amine and/ oracid of the final mixture. Any suitable solvent may be employed and maycomprise an aromatic hydrocarbon such as benzene, toluene, xylene,ethylbenzene, etc., or a mixture such as naphtha, which may be straightrun, catalytically cracked, thermally reformed, catalytically reformed,preferably in the presence of hydrogen or mixtures thereof, kerosene,lubricating oil, etc. Depending upon the particular drawing compositionin which the mixture is employed, the lower boiling solvent may beremoved by fractionation or it may be allowed to remain in the mixture.When desired, the mixture will be marketed as a solution in a suitablesolvent and the same solvent used in the final mixture also may be usedduring the preparation of the amine-carboxylic acid salt.

In general, the neutral salt of the amine and carboxylic acid ispreferred. The neutral salt is prepared by utilizing stoichiometricamounts of the carboxylic acid and amine. In other words, theconcentrations of the car- 3 boxylic acid and amine are selected so thatthere is an equivalent number of carboxylic acid groups to amine groups.In another embodiment the salt may be a basic salt, which is prepared byutilizing a deficiency of carboxylic acid groups in relation to theamino group as, for example, by utilizing one equivalent of carboxylicacid per two equivalents of amine. In still another embodiment, an acidsalt may be employed, which may be prepared by using an excess of acidwith relation to the amine as, for example, two equivalents of acid perone equivalent of amine. Accordingly, the ratio of amine to carboxylicacid may range from 0.2:1 to :1. It is understood that these differentsalts are not necessarily equivalent.

As hereinbefore set forth, another component of the drawing compound ofthe present invention is an amine salt of an alkyl acid phosphate. Theamine preferably is selected from the amines hereinbefore specificallyset forth in the description of the amine salt of carboxylic acid. Inthe interest of simplicity, these amines are not repeated here, but itis understood that the amine is selected from those hereinbeforespecifically set forth.

In one embodiment, the amine used in the preparation of the salt of thealkyl acid phosphate is the same amine as used in the preparation or"the amine salt of the carboxylic acid. In another embodiment, adifferent amine is used in the preparation of each of these salts, butthe amines preferably are selected from those hereinbefore specificallyset forth.

Any suitable alkyl acid phosphate is used in preparing the salt. Theterm alkyl acid phosphate includes both the alkyl acid orthophosphatesand the alkyl acid pyrophosphates. In the alkyl acid orthophosphates,the monoalkyl ester, dialkyl ester or a mixture thereof may be employed.In the alkyl acid pyrophosphate, the monoalkyl ester, dialkyl ester,trialkyl ester or a mixture thereof may be employed, the dialkyl esterbeing preferred and the ester groups being attached to the same ordifferent phosphorus atom. Generally, however, this compound will besymmetrical and, thus, the alkyl ester groups will be attached todifferent phosphorus atoms.

At least one of the alkyl groups constituting the ester portion of thealkyl acid phosphate contains at least 3 and preferably at least 5carbon atoms and may contain up to and preferably up to 12 carbon atoms.Illustrative examples of preferred alkyl acid orthophosphates includemonoamyl acid orthophosphate, diamyl acid orthophosphate, monohexyl acidorthophosphate, dihexyl acid orthophosphate, monoheptyl acidorthophosphate, diheptyl acid orthophosphate, monooctyl acidorthophosphate, dioctyl acid orthophosphate, monononyl acidorthophosphate, dinonyl acid orthophosphate, monodecyl acidorthophosphate, didecyl acid orthophosphate, monoundecyl acidorthophosphate, diundecyl acid orthophosphate, monododecyl acidorthophosphate, didodecyl acid orthophosphate, etc. As hereinbefore setforth, these are the preferred alkyl acid phosphates. However, it isunderstood that the alkyl group or groups may contain from about 3 toabout 20 carbon atoms.

Preferred alkyl acid pyrophosphates include monoamyl acid pyrophosphate,diamyl acid pyrophosphate, monohexyl acid pyrophosphate, dihexyl acidpyrophosphate, monoheptyl acid pyrophosphate, diheptyl acidpyrophosphate, monooctyl acid pyrophosphate, dioctyl acid pyrophosphate,monononyl acid pyrophosphate, dinonyl acid pyrophosphate, monodecyl acidpyrophosphate, didecyl acid pyrophosphate, monoundecyl acidpyrophosphate, diundecyl acid pyrophosphate, monododecyl acidpyrophosphate, didodecyl acid pyrophosphate, etc. Here again, it isunderstood that the alkyl pyrophosphates may contain from about 3 toabout 20 carbon atoms in the alkyl group or groups.

Alkyl acid phosphates are manufactured commercially as a mixture of themonoand di-alkyl acid phosphates and such mixtures generally areavailable at a lower cost. As another advantage of the presentinvention, such lower cost mixtures may be used in preparing the drawingcompound of the present invention. Particularly preferred mixed alkylacid phosphates comprise a mixture of monoand di-isoamyl acidorthophosphate, a mixture of monoand di-isooctyl acid orthophosphate andthe corresponding mixed alkyl acid pyrophosphates.

The amine-alkyl acid phosphate salt is prepared in any suitable manner.In general, this salt is prepared in substantially the same manner asthe amine-carboxylic acid salt as hereinbefore described. The amine andalkyl acid phosphate are commingled, either at ambient temperature orslightly elevated temperature, with vigorous stirring. When an elevatedtemperature is employed, it generally will not exceed about 250 F. Hereagain, a solvent may be used for ease in handling, the solventpreferably being selected from those hereinbefore specifically setforth.

In general, the neutral salt of the alkyl acid phosphate and amine ispreferred. The neutral salt is prepared by utilizing stoichiometricamounts of the alkyl acid phosphate and the amine. In other words, theconcentration of alkyl acid phosphate and amine will be selected so thatthere will be an equivalent number of acid groups to amino groups. Thus,the specific concentrations will depend upon whether the orthophosphateor pyrophosphate salt is prepared and whether a monoamine or polyamineis used. In another embodiment, the salt is a basic salt, which isprepared by utilizing a deficiency of acid groups in relation to theamino group as, for example, by utilizing one equivalent of acid per twoequivalents of amine. In still another embodiment, an acid salt isemployed, which is prepared by using an excess of acid with relation tothe amine as, for example, two equivalents of acid per one equivalent ofamine. Accordingly, the ratio of amine to alkyl acid phosphate may rangefrom 0.2:1 to 5:1. It is understood that these different salts are notnecessarily equivalent.

In the preparations described above, the amine salt of the carboxylicacid and the amine salt of the alkyl acid phosphate are separatelyformed and then are commingled in the desired proportions. In anotherembodiment, the amine salts may be prepared in a single step. In thisembodiment, the carboxylic acid and the alkyl acid phosphate arecomrningled, preferably with vigorous stirring, and then the amine oramines are added thereto with vigorous stirring. The reaction iseffected at ambient temperature, or an elevated temperature whichgenerally will not exceed about 250 F. may be employed. In cases wherethe amine is a solid at ambient temperature, the amine may be heated upto about 250 F. in order to melt the same and the melted amine then isadded to the acids as aforesaid.

The salt of carboxylic acid and the amine salt of alkyl acid phosphateare viscous liquids when prepared in the absence of solvents.Accordingly, for convenience in handling and also for economic reasons,it is preferred that the active ingredients be used in the form of asolution in a suitable solvent and particularly mineral oil. When one orboth of the salts are prepared in the presence of a solvent, preferablythe solvent is retained in the composition and, when desired, additionalsolvent is added to form a composition of the desired consistency. Inthe cold working process, a low boiling, intermediate boiling or highboiling solvent may be used, depending upon the particular workingoperation. In the hot working operation, a high boiling solventpreferably is employed in order to avoid vaporization of the solvent andpossible fire hazard. As hereinbefore set forth, the con sistency of thedrawing composition will vary with each particular machine shop, pressshop, foundry, fabricator, etc., to suit its particular requirements.

The amine salt of carboxylic acid and the amine salt of alkyl acidphosphate generally are used in substantially equal concentrations, butmay be employed in proportions ranging from 0.1 to 10 and particularlyfrom 0.5 to 2 parts by weight of one salt per 1 part by weight of theother salt. The concentration of total active ingredient (total of aminesalt of carboxylic acid and of amine salt of alkyl acid phosphate) inthe final drawing composition may vary considerably. In general, thisconcentration will be in the range of from about 0.1% to about 50% andpreferably from about 0.5% to about by weight of the final composition.

In one embodiment the amine salts are prepared as a concentrate ofactive ingredients and will be dissolved in a solvent in the desiredproportions. In another embodiment the amine salts are prepared as aconcentrated solution in a solvent, and then are diluted further withadditional solvent to the desired concentration. As hereinbefore setforth, the consistency of the final drawing composition will vary withthe particular user to suit his peculiar requirements.

In another embodiment of the invention, the concentrated activeingredients or a concentrated solution thereof may be added to aconventional drawing compound. A large number of conventional drawingcompounds were investigated by the present applicants and found toimpart little or no protection from corrosion. When the activeingredients of the present invention are incorporated in such drawingcompounds, the final drawing compound will afford protection againstcorrosion and also will offer the additional advantages hereinafter setforth. In this embodiment, the drawing compound should contain theactive ingredients of the present invention in a total concentration offrom about 0.5 to about 20% by weight of the final composition.

The drawing compound of the present invention is used in any suitablemanner and generally as conventionally used in the shops. This maycomprise passing the metal to be worked through a layer of the drawingcompound, thereby forming a film of drawing compound on the metal, andthen passing the metal into the working operation. In another embodimenta flowing stream of the drawing composition may be passed over the metaland/ or die before or during the working operation. No novelty isclaimed herein for any particular method of using the drawing compoundand, as hereinbefore set forth, any suitable method may be employed.

Regardless of the method of applying the drawing compound, the novelcomposition of the present invention offers important advantages in theworking operation. As hereinbefore set forth, this composition is aneffective lubricant and also an effective coolant. In addition, thenovel drawing compound of the present invention serves to impartcorrosion protection to both the metal being worked and the die used inthe operation. As hereinbefore set forth, imparting protection fromcorrosion to the metal is important in the further use or workingthereof. Additionally, the drawing compound protects the die fromcorrosion, either during use or during periods of shutdown. It is aconsiderable contribution to the field of drawing compounds that allthree of these important requirements are obtained through the use of asingle composition. This avoids the additional time and expenseheretofore required in utilizing two different compositions and twodifferent treatments to obtain these results.

As another important advantage to the novel drawing compound of thepresent invention, it has been found that the heretofore necessity ofperiodically dressing a die for shallow drawing of close toleranceappears to be eliminated. In other Words, heretofore in such operations,it has been necessary to periodically buff the die with an emery clothto rub out rough spots and scratches. However, when using the noveldrawing compound of the present invention, the dressing operation nolonger is necessary and, in fact, it appears that the die actually seemsto gain in polish.

As another important advantage to the use of the novel drawing compoundof the present invention, it appears to diameter having a peripheralflange of /1".

considerably reduce blow back normally encountered in subsequent castingoperations. Blow back apparently is caused by deposits on objects whichare being subjected to casting. However, it has been found that metalparts formed in the presence of the drawing compound of the presentinvention apparently contain very little or no deposits because blowback is no problem during subsequent casting operations. Therefore, whenthe metal part formed in the presence of the drawing compound of thepresent invention is joined to another part in a casting operation, thereduction or elimination of blow back during the casting operation isanother important advantage.

As still another advantage to the novel drawing compound of the presentinvention, it has been found that there are no objectionable etfectstothe weldability of the formed metal. Therefore, welding of the metal isreadily accomplished when desired. Still another advantage is that themetal part may be painted without objectionable effects. As stillanother advantage, it appears that the use of the drawing compound ofthe present invention results in a cleaner finished part and, therefore,may eliminate subsequent cleaning which otherwise may be required whenusing other drawing compounds.

From the above description, it will be seen that the novel drawingcompound of the present invention offers many advantages over thedrawing compounds presently being used. Of utmost importance is the factthat lubrication, cooling and corrosion prevention are obtained in asingle operation, thereby avoiding the heretofore necessity of requiringtwo separate operations to accomplish this. In addition, other importantadvantages are obtained including protecting the die from corrosion,avoiding blow back, eliminating periodic dressing of the dies,eliminating cleaning of the formed articles, etc.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

Example I The active ingredients of the drawing compound of this examplecomprised by weight of the neutral salt of Duomeen T and DSOME Acid and50% by weight of the neutral salt of Duomeen T and mixed monoanddiisooctyl acid orthophosphates. As hereinbefore set forth, Duomeen T isN-tallow-1,3-diaminopropane and contains predominantly 16 to 18 carbonatoms in the tallow group. Also, as hereinbefore set forth, DSOME Acidis of substantially the same composition as VR1 Acid. The mixed monoanddiisooctyl acid orthophosphates are available commercially.

For ease in handling, the preparation was made in admixture with acommercial paraffinic oil having an API gravity at F. of about 28 and aviscosity at F. of about 108 SUS. The neutral salts were prepared in asingle step operation by dissolving 360 pounds (1 equivalent weight) ofDSOME Acid in 500 pounds of the paraffinic oil and vigorously mixing atambient temperature. 250 pounds (1 equivalent weight) of the mixedmonoand diisooctyl orthophosphates then were added with continuedmixing. Finally, 346 pounds (2 equivalent weights) of Duomeen T wereadded and the vigorous mixing continued until a homogeneous solution wasformed. The concentrate prepared in the above manner then was dilutedwith additional pa-raflinic oil to form a solution containing the activeingredients in a total concentration of 40% by weight.

The concentrated solution described above was diluted further in aproportion of 1 volume of the concentrated solution and 5 volumes ofcommercial paint thinner. The final solution was used as a drawingcompound for the drawing of cold roller steel to form a hub seal. Thisoperation is drawn to a close tolerance and therefore requires a veryeffective drawing compound. A steel disc of 7" diameter was stamped toform a hub seal of 5" The metal disc was dipped into a solution of thedrawing compound described above prior to the stamping operation.

As hereinb'efore set forth, numerous commercial drawlng compounds Wereinvestigated by the present applicants and it was found that none ofthese conventional drawing compounds afiorded corrosion protection tothe finished article. When stored outside, the finished article formedin the presence of the conventional drawing compounds began rustingwithin days.

In contrast to the above, the hub seal formed in the presence of thedrawing compound of the present invention described above did not showany signs of corrosion after more than two months of outdoor storage.

In addition to permitting the close tolerance drawing, the drawingcompound of the present invention protected the die from corrosionduring shutdown. Heretofore, it had been necessary to periodically dressthe surface of the die. This dressing operation consisted of using anemery cloth and rubbing out rough spots and scratches. When using thedrawing compound of the present invention, the dressing operation wasunnecessary and, in fact, the die seemed to gain in polish.

Example II The drawing compound of this example was prepared in themanner described in Example I except using a 1:1 volume dilution withcommercial paint thinner. This drawing compound was used in the coldforming of a part to be integrated with a cast part. As hereinbefore setforth, during the casting a serious problem is the blow back apparentlycaused by deposits on the object being cast. Surprisingly, it was .foundthat blow back was practically eliminated when using the part formed bycold rolling in the presence of the drawing compound of the presentinvention.

Example III The concentrated solution, prepared as described in ExampleI, also was added to a commercial drawing compound. The concentratedsolution Was added in a proportion of 1 volume of concentrated solutionper 5 volumes of the commercial drawing compound.

When used for the forming operation described in Example I, it was foundthat the hub seal formed in the presence of this drawing compoundunderwent no corrosion for a period of two months in outdoor storage. Incontrast, the hub seal formed in the presence of the commercial drawingcompound (not containing the concentrated solution) underwent corrosionwithin 5 days of outdoor storage.

Example IV The drawing compound of this example comprises 5% by Weightof the neutral salt of tallow amine and tall oil acid, 5% by weight ofthe neutral salt of tallow amine and mixed monoand di-isoamyl acidorthophosphates, and 90% by weight of a commercial paraflinic oil. Thesalt of tallow amine and tall oil is prepared by mixing these materialsat room temperature with vigorous stirring. The salt of tallow amine andmixed monoand diisoamyl acid orthophosphates is separately prepared bymixing these materials at room temperature with vigorous stirring. Thesalts then are commingled with the paraflinic oil in the proportionsdescribed above.

The solution described above is used as a drawing compound to form smallmotor cases from cold rolled coil 10 stock. The drawing compound isroller-coat applied to the metal prior to forming. Following the formingoperation, it is found that the parts do not need to be cleaned and thatthey will remain free from corrosion when stored outside prior tofurther processing.

We claim as our invention:

1. The method of working a metal which comprises effecting said workingin contact with a drawing composition consisting essentially of fromabout 0.1% to about 50% by weight of a mixture of (l) a salt of an aminehaving at least 8 carbon atoms and a carboxylic acid having at least 6carbon atoms and (2) a salt of an amine having at least 8 carbon atomsand an alkyl acid phosphate in which at least 1 alkyl group contains atleast 3 carbon atoms, said salts being free of metal and being in theproportion of from about 0.1 to 10 parts by weight of one of the saltsper 1 part by weight of the other salt.

2. The method of claim 1 wherein said salts are dissolved in a mineraloil in a concentration of from about 0.1 to about 50% by weight of thefinal composition.

3. The method of claim 1 wherein said salts are dissolved in a mineraloil in a concentration of from about 0.5 to about 20% by weight of thefinal composition.

4. The method of claim 1 wherein said salts are (1) a salt of a diaminehaving from 8 to about 40 carbon atoms per molecule and a carboxylicacid having from 6 to about 50 carbon atoms per molecule and (2) a saltof a diamine having from 8 to about 40 carbon atoms per molecule and analkyl acid phosphate in which at least 1 alkyl group contains from about3 to about 20 carbon atoms.

5. The method of claim 1 wherein said salts are 1) a salt ofN-alkyl-1,3-diaminoalkane in which said alkyl contains at least 8 carbonatoms and a dicarboxylic acid having at least 6 carbon atoms and (2) asalt of N-alkyl- 1,3-diaminoalkane in which said alkyl contains at least8 carbon atoms and an alkyl acid phosphate in which at least 1 alkylgroup contains at least 3 carbon atoms.

6. The method of claim 1 wherein said salts are (1) a salt ofN-tallow-1,3-diaminopropane and a dicarboxylic acid having from about 10to about 50 carbon atoms and (2) a salt of N-talloW-1,3-diaminopropaneand mixed monoand di-alkyl acid orthophosphates.

7. The method of claim 6 wherein said mixed phosphates are mixed monoanddi-amyl acid orthophosphates.

8. The method of claim 6 wherein said mixed phosphates are mixed monoanddi-octyl acid orthophosphates.

References Cited by the Examiner UNITED STATES PATENTS 2,750,366 6/1936Turinsky 20710.1 2,763,614 9/1956 Cantrell et al. 252-32.5 2,815,32412/1957 Zenftman 25232.5 2,840,498 6/1958 Logne et al. 1486.15 2,848,4148/1958 Chenuicek 25232.5 3,000,820 9/ 1961 Eisenhauer 25232.5

FOREIGN PATENTS 460,485 10/ 1948 Canada.

MARCUS U. LYONS, Primary Exam'iner. W LIAM S H N O xq i n

1. THE METHOD OF WORKING A METAL WHICH COMPRISES EFFECTING SAID WORKINGIN CONTACT WITH A DRAWING COMPOSITION CONSISTING ESSENTIALLY OF FROMABOUT 0.1% TO ABOUT 50% BY WEIGHT OF A MIXTURE OF (1) A SALT OF AN AMINEHAVING AT LEAST 8 CARBON ATOMS AND A CARBOXYLIC ACID HAVING AT LEAST 6CARBON ATOMS AND (2) A SALT OF AN AMINE HAVING AT LEAST 8 CARBON ATOMSAND AN ALKYL ACID PHOSPHATE IN WHICH AT LEAST 1 ALKYL GROUP CONTAINS ATLEAST 3 CARBON ATOMS, SAID SALTS BEING FREE OF METAL AND BEING INPROPORTION OF FROM ABOUT 0.1 TO 10 PARTS BY WEIGHT OF ONE OF THE SALTSPER 1 PART BY WEIGHT OF THE OTHER SALT.